CN113929112A - ATS type silicon-aluminum molecular sieve, preparation method and application thereof - Google Patents

ATS type silicon-aluminum molecular sieve, preparation method and application thereof Download PDF

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CN113929112A
CN113929112A CN202010607251.1A CN202010607251A CN113929112A CN 113929112 A CN113929112 A CN 113929112A CN 202010607251 A CN202010607251 A CN 202010607251A CN 113929112 A CN113929112 A CN 113929112A
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molecular sieve
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aluminum
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CN113929112B (en
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杨为民
王振东
刘闯
李相呈
梁俊
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract

The invention discloses an ATS type silicon-aluminum molecular sieve, a preparation method and application thereof. The molecular sieve has the formula of SiO2·1/nAl2O3"a schematic chemical composition shown, wherein the molar ratio of Si to Al is 6. ltoreq. n.ltoreq.10. The molecular sieve has a strip or rod shape, the average length of crystals is 0.6-1.8 mu m, and the length-width ratio is 2-20. The molecular sieve can be used as an adsorbent or a catalyst for organic compound conversion, and has good performance.

Description

ATS type silicon-aluminum molecular sieve, preparation method and application thereof
Technical Field
The invention relates to an ATS type silicon-aluminum molecular sieve, a preparation method and application thereof.
Background
The ATS type molecular sieve is a molecular sieve with one-dimensional twelve-membered ring channels, the pore diameter is 0.65 multiplied by 0.75nm, and the framework of the molecular sieve is made of AlO4Tetrahedron and PO4The tetrahedrons are linked alternately. Metal atoms are introduced into the molecular sieve framework to generate an acid center or an oxidation-reduction center, so that the molecular sieve framework has potential application value in the field of catalysis.
Shyamal Kumar Saha et al with tri-n-propylamine Pr3N is a structure directing agent to synthesize the ATS type molecular sieve, but the synthesis process is complex, two crystallization processes are often needed, and AFI mixed phases are often mixed in the product. Chan et al use a [1- (3-fluorophenyl) cyclopentyl group with a very complex molecular structure]Methyl-trimethyl ammonium compounds are used as structure directing agents to synthesize the ATS type molecular sieve, but the structure directing agents are expensive, and the cost of the molecular sieve is high. Patent WO2001066464a2 uses phenyl cycloalkyl methyl ammonium compound or N-cyclohexyl-N- (2-methyl propyl) pyrrolidinyl compound as a structure directing agent to synthesize a silicon-containing ATS type molecular sieve such as pure silicon, silicon aluminum, silicon boron, silicon titanium, silicon vanadium, etc., and alkali metal elements or alkaline earth metals are required to be added into the synthesis system, and ammonium ion exchange is required to perform a catalytic reaction.
In the preparation of the ATS type molecular sieve, it is basically necessary to add alkali sources such as sodium hydroxide, potassium hydroxide, organic bases, etc., or to add a certain amount of seed crystals to promote crystallization of the molecular sieve, and the post-treatment requires a large amount of water and ammonium ion exchange to obtain the molecular sieve catalyst product. The product prepared in the prior art is basically an ATS type molecular sieve composed of pure silicon, phosphorus aluminum or metal phosphorus aluminum and the like, the related reports of the ATS type molecular sieve composed of silicon and aluminum are less, and the silicon-aluminum ratio is higher. At present, the ATS type molecular sieve is mainly synthesized under hydrothermal conditions, and needs to be crystallized in solvents such as aqueous solution and the like to obtain the ATS type molecular sieve.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel molecular sieve with an ATS structure and a preparation method thereof.
The invention provides an ATS type silicon-aluminum molecular sieve in a first aspect, which is characterized in that the calcined form of the molecular sieve has a formula of SiO2·1/nAl2O3"wherein the molar ratio of Si to Al is 6. ltoreq. n.ltoreq.10, preferably 6.25. ltoreq. n.ltoreq.9.75, more preferably 6.5. ltoreq. n.ltoreq.9.5.
Furthermore, the ATS type silicon-aluminum molecular sieve has a long strip shape or a rod shape, the average length of crystals is 0.6-1.8 μm, and the length-width ratio is 2-20.
Further, the amount of B acid (Bronsted acid) in the ATS type silicon-aluminum molecular sieve is not less than 500 mu mol/g, preferably 500-700 mu mol/g; the amount of the strong B acid is not less than 250 mu mol/g, and preferably 250 to 350 mu mol/g.
Further, the total acid amount of the ATS type silicon-aluminum molecular sieve is not less than 1000 mu mol/g, preferably 1000-1700 mu mol/g, and the strong acid amount is not less than 300 mu mol/g, preferably 300-400 mu mol/g.
Further, the specific surface area of the ATS type silicon-aluminum molecular sieve is 200-600 m2Per gram, preferably 250 to 500 m2Per gram; the micropore volume of the ATS type silicon-aluminum molecular sieve is 0.05-0.30 cm3A/g, preferably 0.10 to 0.25 cm3Per gram.
The second aspect of the invention also provides a preparation method of the ATS type silicon-aluminum molecular sieve, which comprises the steps of mixing a silicon source, an aluminum source, a fluorine source, an organic structure directing agent and water, and then carrying out water steaming treatment; then carrying out crystallization reaction on the raw material mixture to obtain the ATS type silicon-aluminum molecular sieve;
wherein the added silicon source is SiO2Calculated as Al), an aluminum source (calculated as Al)2O3Calculated by the formula) is 1 (0.08-0.17), preferably 1 (0.1-0.15); the organic structure directing agent is preferably 4-pyrrolidinylpyridine.
Further, the added silicon source (in SiO)2The molar ratio of the fluorine source (counted as F), the organic structure directing agent and the water is 1 (0.05-2.0) (0.05-1.0) (7.5-100), preferably 1 (0.1-1.8) (0.1-0.9) (7.5-80), more preferably 1 (0.2-1.6) (0.2-0.8) (7.5-60).
Further, the silicon source is selected from at least one of silicic acid, silica gel, silica sol, tetraethyl silicate and water glass; the aluminum source is selected from at least one of aluminum hydroxide, aluminum oxide, aluminate, aluminum salt and tetraalkoxy aluminum; the fluorine source is preferably hydrofluoric acid.
Further, the water evaporation treatment method comprises rotary evaporation water removal or open heating water removal, wherein the open heating treatment condition is heating and stirring at 35-90 ℃, preferably at 40-85 ℃.
Further, after the raw material mixture is subjected to water evaporation treatment, a silicon Source (SiO) is used for crystallization2Calculated in terms of the total weight of the water-soluble polymer) and water in a molar ratio of 1 (1-5), preferably 1 (1.5-4.5).
Further, the crystallization reaction is performed under the conditions of 120-210 ℃ for 2-20 days, preferably at 130-195 ℃ for 3-18 days, and more preferably at 140-180 ℃ for 4-16 days.
Further, the mixture does not comprise an alkali source.
The third aspect of the invention also provides a molecular sieve composition comprising an ATS-type silicoaluminophosphate molecular sieve according to any one of the preceding aspects or an ATS-type silicoaluminophosphate molecular sieve produced according to the production method of any one of the preceding aspects, and a binder.
The fourth aspect of the invention also provides the use of the ATS-type silicoaluminophosphate molecular sieve according to any of the preceding aspects, and the ATS-type silicoaluminophosphate molecular sieve composition produced by the production method according to any of the preceding aspects, as an adsorbent or a catalyst for conversion of organic compounds.
Use of the ATS-type silicoaluminophosphate molecular sieve according to any of the preceding aspects, the ATS-type silicoaluminophosphate molecular sieve produced by the production method according to any of the preceding aspects, or the ATS-type silicoaluminophosphate molecular sieve composition according to any of the preceding aspects as a catalyst for isomerization reaction of alkane, a catalyst for alkylation reaction of aromatic hydrocarbon and olefin, a catalyst for isomerization reaction of olefin, a catalyst for cracking reaction of naphtha, a catalyst for alkylation reaction of aromatic hydrocarbon and alcohol, a catalyst for hydration reaction of olefin, a catalyst for reaction of olefin reaction by alcohol, and a catalyst for disproportionation reaction of aromatic hydrocarbon.
According to the invention, the related silicon-aluminum molecular sieve has an ATS structure, the silicon-aluminum ratio of the molecular sieve is low, and the chemical composition of the molecular sieve is never obtained in the prior art.
According to the invention, the calcined form of the ATS type silicon-aluminum molecular sieve has special acid properties, the molecular sieve has high acid content and high acid strength, and the strong acid is basically Bronsted acid.
According to the preparation method, the pyrrolidinyl pyridine is used as the organic structure directing agent, alkali does not need to be added in the reaction process, and the obtained molecular sieve can be used as a catalyst without ammonium ion exchange.
According to the preparation method, the raw materials are crystallized in a solid or semi-solid state, and the actual utilization rate of the reaction kettle is higher (more molecular sieve products are finally obtained in the reaction kettle in unit volume).
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 1;
FIG. 2 is a Scanning Electron Micrograph (SEM) of the molecular sieve obtained in example 1;
FIG. 3 is a pyridine adsorption infrared spectrum (Py-IR) of the molecular sieve obtained in example 1;
FIG. 4 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 2;
FIG. 5 is a Scanning Electron Micrograph (SEM) of the molecular sieve obtained in example 2;
FIG. 6 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 3;
FIG. 7 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 4;
FIG. 8 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 5;
FIG. 9 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 8;
FIG. 10 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 9;
fig. 11 is an X-ray diffraction pattern (XRD) of the sample obtained in comparative example 1.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
In the context of the present specification, a molecular sieve is referred to as a "precursor" before substances (such as organic structure directing agent molecules and the like) filled in the channels when the molecular sieve is synthesized, other than water and metal ions, in the channels of the molecular sieve are not removed.
In the context of the present specification, the structure of a molecular sieve is determined by X-ray diffraction pattern (XRD), which is determined by X-ray powder diffractometry using a Cu-ka radiation source, a nickel filter. Before the sample is tested, a Scanning Electron Microscope (SEM) is adopted to observe the crystallization condition of the molecular sieve sample, the sample is confirmed to contain only one crystal, namely the molecular sieve sample is a pure phase, and then XRD test is carried out on the basis, so that no interference peak of other crystals exists in a diffraction peak in an XRD spectrogram.
The invention relates to an ATS type silicon-aluminum molecular sieve, a preparation method and application thereof.
According to the present invention, the ATS-type aluminosilicate molecular sieve may exist in an unfired state (synthesized state) or in a calcined state. When present in the as-synthesized state, the ATS-type aluminosilicate molecular sieves generally have a schematic chemical composition as represented by the formula "oxide-organic structure directing agent-water". In the case of presence in the calcined state, it is known that molecular sieves sometimes (especially immediately after synthesis) contain some amount of moisture, but it is not considered necessary to specify this amount of moisture in the present invention because the presence or absence of this moisture does not substantially affect the XRD pattern of the molecular sieve.
According to the present invention, in a schematic chemical composition represented by the formula "oxide-organic structure directing agent-water", the m ratio of the organic structure directing agent to the oxide is 0.01 to 2.0, preferably 0.03 to 0.40, more preferably 0.05 to 0.33, more preferably 0.06 to 0.30, more preferably 0.07 to 0.21.
According to the invention, in the schematic chemical composition represented by the formula "oxide-organic structure directing agent-water", the mass ratio of the water to the oxide is 0 to 0.17, preferably 0.02 to 0.12.
According to the invention, in the synthesis method of the molecular sieve, the oxide is SiO2And Al2O3Combinations of (a) and (b).
According to the invention, the molecular sieve has a form after calcination as shown in formula SiO2·1/nAl2O3"wherein the molar ratio of Si to Al is 6. ltoreq. n.ltoreq.10, preferably 6.25. ltoreq. n.ltoreq.9.75, more preferably 6.5. ltoreq. n.ltoreq.9.5.
Further, the mole ratio of Si to Al within the value range of 6 ≦ n ≦ 10 may be 6.25, 6.50, 6.70, 6.80, 7.00, 7.20, 7.5, 7.90, 8.00, 8.20, 8.40, 8.60, 8.80, 9.00, 9.10, 9.20, 9.30, 9.40, 9.50, 9.60, 9.70, 9.80, 9.90.
According to the invention, the ATS type silicon-aluminum molecular sieve has a special long strip shape or a rod shape, the average length of crystals is 0.6-1.8 mu m, and the length-width ratio is 2-20.
Further, the amount of B acid (Bronsted acid) in the ATS type silicon-aluminum molecular sieve is not less than 500 mu mol/g, preferably 500-700 mu mol/g; the amount of the strong B acid is not less than 250 mu mol/g, and preferably 250 to 350 mu mol/g.
Further, the total acid amount of the ATS type silicon-aluminum molecular sieve is not less than 1000 mu mol/g, preferably 1000-1700 mu mol/g, and the strong acid amount is not less than 300 mu mol/g, preferably 300-400 mu mol/g.
According to the invention, the specific surface area of the ATS type silicon-aluminum molecular sieve is 200-600 m2Per gram, preferably 250 to 500 m2Per gram; the micropore volume of the ATS type silicon-aluminum molecular sieve is 0.05-0.30 cm3A/g, preferably 0.10 to 0.25 cm3Per gram.
According to the present invention, the ATS type silicoaluminophosphate molecular sieve can be synthesized by the following synthesis method. In view of this, the present invention also relates to a method for synthesizing an ATS-type aluminosilicate molecular sieve, comprising a step of crystallizing a mixture (hereinafter, simply referred to as a mixture) comprising a silicon source, an aluminum source, an organic structure directing agent, a fluorine source, and water under crystallization conditions to obtain the molecular sieve (hereinafter, referred to as a crystallization step).
In the method for synthesizing the molecular sieve according to the present invention, the crystallization step may be performed in any manner conventionally known in the art, such as a method of mixing the oxide source, the organic structure directing agent, the fluorine source and water in a predetermined ratio, distilling off a part of water, and crystallizing the obtained mixture by heating under crystallization conditions.
According to the invention, in the synthesis method of the molecular sieve, the silicon source is (SiO2Calculated as Al) and an aluminum source (calculated as Al)2O3By weight) are as follows: 1 (0.08-0.17), preferably 1 (0.1-0.15).
According to the invention, in the synthesis method of the molecular sieve, the silicon source is (SiO2To count),The molar ratio of the fluorine source (counted as F), the organic structure directing agent and the water is 1 (0.05-2.0), (0.05-1.0), (7.5-100), preferably 1 (0.1-1.8), (0.1-0.9), (7.5-80), more preferably 1 (0.2-1.6), (0.2-0.8), (7.5-60).
According to the invention, in the synthesis method of the molecular sieve, the silicon source is selected from at least one of silicic acid, silica gel, silica sol, tetraethyl silicate and water glass; the aluminum source is selected from at least one of aluminum hydroxide, aluminum oxide, aluminate, aluminum salt and tetraalkoxy aluminum; the fluorine source is preferably hydrofluoric acid.
According to the invention, the method for treating the distilled water is rotary evaporation water removal or open heating water removal, and the treatment condition of the open heating is heating and stirring at 35-90 ℃, preferably at 40-85 ℃.
According to the invention, the raw material mixture is crystallized after being treated by distilled water, and the silicon source (SiO is used as the silicon source)2Calculated in terms of the total weight of the water-soluble polymer) and water in a molar ratio of 1 (1-5), preferably 1 (1.5-4.5).
According to the invention, the crystallization condition of the mixture is crystallization at 120-210 ℃ for 2-20 days, preferably crystallization at 130-195 ℃ for 3-18 days, and more preferably crystallization at 140-180 ℃ for 4-16 days.
According to one embodiment of the present invention, in the synthesis method of the molecular sieve, the mixture does not contain an alkali source from the viewpoint of more favorable obtainment of the ATS-type aluminosilicate molecular sieve of the present invention. Examples of the alkali source include alkaline substances other than a silicon source, an aluminum source and an organic structure directing agent, and specific examples thereof include any alkali source conventionally used in the art for the purpose of making the system alkaline, and more specific examples thereof include inorganic bases having an alkali metal or an alkaline earth metal as a cation, and in particular, sodium hydroxide, potassium hydroxide and the like. Herein, "not including an alkali source" means that an alkali source is not intentionally or actively introduced into the mixture.
According to the present invention, after the crystallization step is completed, the molecular sieve product may be separated from the resulting mixture by any separation means conventionally known. The separation method includes, for example, a method of filtering, washing and drying the obtained mixture. Here, the filtering, washing and drying may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply filtered with suction. Examples of the washing include washing with deionized water and/or ethanol. The drying temperature is, for example, 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours. The drying may be carried out under normal pressure or under reduced pressure.
According to the invention, the molecular sieve prepared according to the method described above can also be calcined to remove the template agent and possibly the water, etc. The calcination can be carried out in any manner conventionally known in the art, for example, the calcination temperature is generally 300 to 800 ℃, preferably 400 to 650 ℃, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
The method synthesizes the high-purity ATS type silicon-aluminum molecular sieve, the silicon-aluminum ratio of the molecular sieve is low, the chemical composition of the molecular sieve is never obtained before in the field, and the molecular sieve has a strip shape or a rod shape. The calcined ATS type silicon-aluminum molecular sieve has special acid property, the molecular sieve has high acid content and high acid strength, and the strong acid is basically Bronsted acid. The preparation method adopts the pyrrolidinyl pyridine as an organic structure directing agent, does not need to add alkali in the reaction process, and can be directly used for catalysis without ammonium ion exchange; the mixture is crystallized in a solid or semi-solid state, and the actual utilization rate of the reaction kettle is higher (more molecular sieve products are finally obtained in the reaction kettle with unit volume). The method is simple, the raw materials are cheap, and the method is suitable for large-scale industrial production and has a good technical effect.
In the context of the present specification, including the following examples and comparative examples, the pore volume and specific surface area of the molecular sieve are measured by nitrogen physical adsorption and desorption (BET method): the nitrogen physical adsorption and desorption isotherm of the molecular sieve is measured by a physical adsorption instrument (micromeric ASAP2020M physical adsorption instrument), and then calculated by a BET equation and a t-plot equation. The experimental conditions for the ATS type silicoaluminophosphate molecular sieve were: the measurement temperature was-169 ℃, the molecular sieves were vacuum pretreated at 350 ℃ for 4 hours before measurement, and the experimental conditions for the molecular sieves were: the measurement temperature is-169 ℃, the molecular sieve is firstly subjected to heat treatment for 6 hours at 550 ℃ in air atmosphere before measurement, and then is subjected to vacuum pretreatment for 4 hours at 350 ℃.
In the context of the present specification, including in the examples and comparative examples below, a temperature programmed desorption apparatus (NH) for molecular sieves3TPD) is Altamira Instruments AMI-3300, and the specific test method is as follows: pretreating a molecular sieve for 1 hour at 550 ℃ in helium atmosphere, and adsorbing NH at 100 DEG C3Mixed gas of/He, then raising the temperature from 100 ℃ to 600 ℃ for NH3Desorbing, and detecting a peak by TCD; the acid content of the molecular sieve was quantitatively calculated by the software, wherein a signal peak above 350 ℃ could be considered as a strong acid. In the context of the present description, including in the following examples and comparative examples, the X-ray powder diffractometer model of the molecular sieve is the Panalytical X PERPRO model X-ray powder diffractometer, the phase of the sample is analyzed, CuK alpha ray source
Figure BDA0002559587660000071
The 2 theta scanning range of the nickel filter is 2-50 degrees, the operating voltage is 40KV, the current is 40mA, and the scanning speed is 10 degrees/min.
In the context of the present specification, including the examples and comparative examples below, the molecular sieve is a Scanning Electron Microscope (SEM) model S-4800 type II field emission SEM.
In the context of the present specification, including the following examples and comparative examples, the molecular sieve was analyzed by inductively coupled plasma atomic emission spectrometry (ICP) model Varian 725-ES, and the content of the element was measured by dissolving the sample with hydrofluoric acid.
In the context of the present specification, including in the following examples and comparative examples, the method of measuring the crystal length and width of a molecular sieve is: molecular sieves were observed using a transmission electron microscope (e.g., FEI G2F30 transmission electron microscope, operating at 300kV) at 10 ten thousand times magnification, randomly selecting an observation field, calculating the average of the sum of the lengths of all crystals in the observation field, and calculating the average of the sum of the widths of all crystals in the observation field, and repeating the operation a total of 10 times. The average of the sum of the average of 10 times was taken as the crystal length and width.
The acid amount and acid type of the molecular sieve are measured by a pyridine adsorption infrared method (Nicolet Model 710 spectrometer). The specific operation steps are as follows: a. and (4) sample pretreatment. The samples (about 30mg) were tabletted into thin disks of 13mm diameter and loaded into infrared sample cells. Thereafter, the samples were pretreated for 1h under vacuum cell conditions at 400 ℃. When the sample tank is cooled to room temperature, the infrared data of the sample is scanned as background. b. And (4) pyridine adsorption. And (3) introducing pyridine vapor to the original position at room temperature and in a vacuum environment until the adsorption reaches the equilibrium, wherein the adsorption time is 1 h. c. And (4) desorbing the pyridine. After adsorption, vacuumizing at 100 ℃ until the internal pressure does not change, wherein the desorption time is 40min, and scanning and recording infrared absorption spectra respectively. The difference spectrum before and after pyridine adsorption is the obtained pyridine adsorption-infrared absorption spectrogram. The acid amount of the sample was calculated semi-quantitatively according to the profile:
Figure BDA0002559587660000081
wherein r and w are the diameter (cm) and mass (g) of a thin disk of the catalyst, and A is the integrated value of absorbance at a given wavenumber peak according to a scanning pyridine adsorption-infrared absorption spectrum. IMEC is the integral molar extinction coefficient, IMECLIs 2.22, IMECBWas 1.67. 1545cm-1The nearby peak is B acid, 1455cm-1The nearby peak is L acid, wherein the peak of B acid obtained after pyridine desorption at 400 ℃ can be regarded as strong B acid, and the acid amount corresponding to the spectrum is the acid amount of the strong B acid.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Example 1
5.801 g of deionized water, 7.161 g of organic structure directing agent 4-pyrrolidinylpyridine, 14.515 g of silica sol (containing SiO)240 percent by weight), 3.9474 grams of aluminum isopropoxide and 4.834 grams of hydrofluoric acid (containing 40 percent by weight of HF) are uniformly mixed, the mixture is stirred at room temperature for 2 hours, then the raw material liquid is stirred at 80 ℃ in an open way, 9.05 grams of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al2O3/SiO2＝0.10
4-Pyrrolidinopyridine/SiO2＝0.5
F/SiO2＝1.0
H2O/SiO2＝4.8
The mixture was put into a stainless steel reaction vessel and crystallized at 170 ℃ for 14 days. Filtering, washing, and drying in a 110 deg.C oven to obtain molecular sieve with XRD spectrogram shown in figure 1, which is ATS silicon-aluminum type molecular sieve; the SEM image of the molecular sieve is shown in FIG. 2, the molecular sieve is in a strip shape, the average length of the crystal is 1 μm, and the aspect ratio is 9; the pyridine adsorption infrared Py-IR spectrogram after molecular sieve calcination is shown in FIG. 3, the acid B amount is 600. mu. mol/g, and the strong acid B amount is 300. mu. mol/g; NH (NH)3TPD found the total acid content of the sieve to be 1500. mu. mol/g, and the strong acid content to be 350. mu. mol/g.
The specific surface area of the obtained product is 459 m2G, micropore volume of 0.16 cm3Per gram.
Measuring SiO of sample by inductively coupled plasma atomic emission spectrometry (ICP)2/Al2O3＝9.8。
Example 2
13.339 g of deionized water, 11.974 g of organic structure directing agent 4-pyrrolidinylpyridine, 20.226 g of silica sol (containing SiO)240 percent by weight), 5.5007 g of aluminum isopropoxide and 6.063 g of hydrofluoric acid (containing 40 percent by weight of HF) are uniformly mixed, the mixture is stirred at room temperature for 2 hours, then the raw material liquid is stirred at 65 ℃ in an open way, 18.44 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al2O3/SiO2＝0.10
4-Pyrrolidinopyridine/SiO2＝0.6
F/SiO2＝0.9
H2O/SiO2＝4.4
The mixture was put into a stainless steel reaction vessel and crystallized at 160 ℃ for 12 days. Filtering, washing, and drying in a 110 deg.C oven to obtain molecular sieve with XRD spectrogram shown in FIG. 4, which is ATS type silicon aluminum molecular sieve; the SEM image of the molecular sieve is shown in FIG. 5, the molecular sieve is rod-like, the average length of the crystal is 0.8 μm, and the aspect ratio is 7; the pyridine adsorption infrared Py-IR spectrogram after molecular sieve calcination is similar to that in FIG. 3, the acid B amount is 600 mu mol/g, and the strong acid B amount is 300 mu mol/g; NH (NH)3TPD determined as 1450. mu. mol/g total acid and 320. mu. mol/g strong acid.
The specific surface area of the obtained product is 466 m2G, micropore volume of 0.16 cm3Per gram.
Measuring SiO of sample by inductively coupled plasma atomic emission spectrometry (ICP)2/Al2O3＝9.7。
Example 3
15.930 g of deionized water, 14.979 g of organic structure directing agent 4-pyrrolidinylpyridine, 18.977 g of silica sol (containing SiO)240 percent by weight), 5.1608 grams of aluminum isopropoxide and 7.584 grams of hydrofluoric acid (containing 40 percent by weight of HF) are uniformly mixed, the mixture is stirred at room temperature for 2 hours, then the raw material liquid is stirred at 70 ℃ in an open way, 22.76 grams of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al2O3/SiO2＝0.10
4-Pyrrolidinopyridine/SiO2＝0.8
F/SiO2＝1.2
H2O/SiO2＝4.0
The mixture was put into a stainless steel reaction vessel and crystallized at 150 ℃ for 14 days. Filtering, washing, and drying in a 110 deg.C oven to obtain molecular sieve with XRD spectrogram shown in FIG. 6, which is ATS type silicon aluminum molecular sieve; the SEM image of the molecular sieve is similar to that of FIG. 2, the molecular sieve is in a strip shape, the average length of the crystal is 0.7 μm, and the length-width ratio is 8; pyridine adsorption red after molecular sieve roastingThe outer Py-IR spectrum is similar to that of FIG. 3, with 600. mu. mol/g acid B and 300. mu. mol/g strong acid B; NH (NH)3TPD found the total acid content of the sieve to be 1350. mu. mol/g and the strong acid content to be 330. mu. mol/g. The specific surface area of the product obtained was 448 m2G, micropore volume of 0.16 cm3Per gram.
Measuring SiO of sample by inductively coupled plasma atomic emission spectrometry (ICP)2/Al2O3＝9.9。
Example 4
18.882 g of deionized water, 6.484 g of organic structure directing agent 4-pyrrolidinylpyridine, 16.430 g of silica sol (containing SiO)240 percent by weight), 4.6915 grams of aluminum isopropoxide and 4.651 grams of hydrofluoric acid (containing 40 percent by weight of HF) are uniformly mixed, the mixture is stirred at room temperature for 2 hours, then the raw material liquid is stirred at 85 ℃ in an open way, 22.47 grams of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al2O3/SiO2＝0.105
4-Pyrrolidinopyridine/SiO2＝0.4
F/SiO2＝0.85
H2O/SiO2＝4.6
The mixture was put into a stainless steel reaction vessel and crystallized at 180 ℃ for 7 days. Filtering, washing, and drying in a 110 deg.C oven to obtain molecular sieve with XRD spectrogram shown in FIG. 7, which is ATS type silicon aluminum molecular sieve; the SEM image of the molecular sieve is similar to that of FIG. 2, the molecular sieve is in a strip shape, the average length of the crystal is 1.2 μm, and the aspect ratio is 7; the pyridine adsorption infrared Py-IR spectrogram after molecular sieve calcination is similar to that in FIG. 3, the acid B amount is 600 mu mol/g, and the strong acid B amount is 300 mu mol/g; NH (NH)3The total acid content of the sieve, determined as TPD, was 1400. mu. mol/g and the strong acid content was 325. mu. mol/g. The specific surface area of the product obtained was 455 m2G, micropore volume of 0.15 cm3Per gram.
Measuring SiO of sample by inductively coupled plasma atomic emission spectrometry (ICP)2/Al2O3＝9.5。
Example 5
16.647 g of deionized water and 8.137 g of organic junctionThe structure directing agent 4-pyrrolidinylpyridine 16.493 g of silica sol (containing SiO)240 percent by weight), 4.9339 g of aluminum isopropoxide and 5.218 g of hydrofluoric acid (containing 40 percent by weight of HF) are uniformly mixed, the mixture is stirred at room temperature for 2 hours, then the raw material liquid is stirred at 80 ℃ in an open way, 21.37 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al2O3/SiO2＝0.11
4-Pyrrolidinopyridine/SiO2＝0.5
F/SiO2＝0.95
H2O/SiO2＝4.2
The mixture was put into a stainless steel reaction vessel and crystallized at 175 ℃ for 8 days. Filtering, washing, and drying in a 110 deg.C oven to obtain molecular sieve with XRD spectrogram shown in FIG. 8, which is ATS type silicon aluminum molecular sieve; the SEM image of the molecular sieve is similar to that of FIG. 2, the molecular sieve is in a strip shape, the average length of the crystal is 1 μm, and the length-width ratio is 8; the pyridine adsorption infrared Py-IR spectrogram after molecular sieve calcination is similar to that in FIG. 3, the acid B amount is 600 mu mol/g, and the strong acid B amount is 300 mu mol/g; NH (NH)3TPD found the total acid content of the sieve to be 1330. mu. mol/g, the strong acid content to be 310. mu. mol/g. The specific surface area of the obtained product was 475 m2G, micropore volume 0.17 cm3Per gram.
Measuring SiO of sample by inductively coupled plasma atomic emission spectrometry (ICP)2/Al2O3＝9.2。
Example 6
17.903 g of deionized water, 5.892 g of organic structure directing agent 4-pyrrolidinylpyridine, 13.269 g of silica sol (containing SiO)240 percent by weight), 4.3304 g of aluminum isopropoxide and 4.640 g of hydrofluoric acid (containing 40 percent by weight of HF) are uniformly mixed, the mixture is stirred at room temperature for 2 hours, then the raw material liquid is stirred at 85 ℃ in an open way, 23.56 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al2O3/SiO2＝0.12
4-Pyrrolidinopyridine/SiO2＝0.45
F/SiO2＝1.05
H2O/SiO2＝3.2
The mixture was put into a stainless steel reaction vessel and crystallized at 170 ℃ for 9 days. Filtering, washing, and drying in a 110 deg.C oven to obtain molecular sieve with XRD spectrogram similar to that of FIG. 1, which is ATS type silicon-aluminum molecular sieve; the SEM image of the molecular sieve is similar to that of FIG. 2, the molecular sieve is in a strip shape, the average length of the crystal is 0.8 μm, and the length-width ratio is 6; the pyridine adsorption infrared Py-IR spectrogram after molecular sieve calcination is similar to that in FIG. 3, the acid B amount is 600 mu mol/g, and the strong acid B amount is 300 mu mol/g; NH (NH)3TPD found the total acid content of the sieve was 1180. mu. mol/g, with a strong acid content of 310. mu. mol/g.
The specific surface area of the resulting product was 432 m2G, micropore volume of 0.15 cm3Per gram.
Measuring SiO of sample by inductively coupled plasma atomic emission spectrometry (ICP)2/Al2O3＝8.6。
Example 7
9.899 g of deionized water, 8.585 g of organic structure directing agent 4-pyrrolidinylpyridine, 13.386 g of silica sol (containing SiO)240 percent by weight), 4.7327 g of aluminum isopropoxide and 4.904 g of hydrofluoric acid (containing 40 percent by weight of HF) are uniformly mixed, the mixture is stirred at room temperature for 2 hours, then the raw material liquid is stirred at 60 ℃ in an open way, 16.06 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al2O3/SiO2＝0.13
4-Pyrrolidinopyridine/SiO2＝0.65
F/SiO2＝1.1
H2O/SiO2＝3
The mixture was put into a stainless steel reaction vessel and crystallized at 165 ℃ for 10 days. Filtering, washing, and drying in a 110 deg.C oven to obtain molecular sieve with XRD spectrogram similar to that of FIG. 1, which is ATS type silicon-aluminum molecular sieve; the SEM image of the molecular sieve is similar to that of FIG. 2, the molecular sieve is in a strip shape, the average length of the crystal is 0.6 μm, and the aspect ratio is 7; the pyridine adsorption infrared Py-IR spectrogram after molecular sieve calcination is similar to that in FIG. 3, the acid B amount is 600 mu mol/g, and the strong acid B amount is 300 mu mol/g; NH (NH)3TPD measurement of the moleculeThe total acid content of the sieve was 1230. mu. mol/g, the strong acid content was 315. mu. mol/g. The specific surface area of the obtained product was 446 m2G, micropore volume of 0.16 cm3Per gram.
Measuring SiO of sample by inductively coupled plasma atomic emission spectrometry (ICP)2/Al2O3＝8.2。
Example 8
4.103 grams of deionized water, 7.666 grams of organic structure directing agent 4-pyrrolidinylpyridine, 11.100 grams of silica sol (containing SiO)240 percent by weight), 4.2261 g of aluminum isopropoxide and 4.251 g of hydrofluoric acid (containing 40 percent by weight of HF) are uniformly mixed, the mixture is stirred at room temperature for 2 hours, then the raw material liquid is stirred at 50 ℃ in an open way, 8.25 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al2O3/SiO2＝0.14
4-Pyrrolidinopyridine/SiO2＝0.7
F/SiO2＝1.15
H2O/SiO2＝3.8
The mixture was put into a stainless steel reaction vessel and crystallized at 145 ℃ for 13 days. Filtering, washing, and drying in a 110 deg.C oven to obtain molecular sieve with XRD spectrogram shown in FIG. 9, which is ATS type silicon aluminum molecular sieve; the SEM image of the molecular sieve is similar to that of FIG. 2, the molecular sieve is in a strip shape, the average length of the crystal is 1.2 μm, and the length-width ratio is 8; the pyridine adsorption infrared Py-IR spectrogram after molecular sieve calcination is similar to that in FIG. 3, the acid B amount is 600 mu mol/g, and the strong acid B amount is 300 mu mol/g; NH (NH)3TPD found the total acid content of the sieve to be 1620. mu. mol/g and the strong acid content to be 368. mu. mol/g. The specific surface area of the resulting product was 439 m2G, micropore volume of 0.16 cm3Per gram.
Measuring SiO of sample by inductively coupled plasma atomic emission spectrometry (ICP)2/Al2O3＝7.9。
Example 9
15.831 g of deionized water, 13.433 g of organic structure directing agent 4-pyrrolidinylpyridine, 24.754 g of silica sol (containing SiO)240% by weight), 10.098 g of aluminum isopropoxide, 8244 g of hydrofluoric acid (containing 40 wt% of HF) are mixed uniformly, the mixture is stirred for 2 hours at room temperature, then the raw material liquid is stirred in an open way at 85 ℃, 25.24 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al2O3/SiO2＝0.15
4-Pyrrolidinopyridine/SiO2＝0.55
F/SiO2＝1.0
H2O/SiO2＝3.5
The mixture was put into a stainless steel reaction vessel and crystallized at 155 ℃ for 11 days. Filtering, washing, and drying in a 110 deg.C oven to obtain molecular sieve with XRD spectrogram shown in FIG. 10, which is ATS type silicon aluminum molecular sieve; the SEM image of the molecular sieve is similar to that of FIG. 2, the molecular sieve is in a strip shape, the average length of the crystal is 1.2 μm, and the aspect ratio is 10; the pyridine adsorption infrared Py-IR spectrogram after molecular sieve calcination is similar to that in FIG. 3, the acid B amount is 600 mu mol/g, and the strong acid B amount is 300 mu mol/g; NH (NH)3TPD measured the total acid content of the sieve at 1480. mu. mol/g, with a strong acid content of 325. mu. mol/g.
The specific surface area of the resulting product was 431 m2G, micropore volume of 0.16 cm3Per gram.
Measuring SiO of sample by inductively coupled plasma atomic emission spectrometry (ICP)2/Al2O3＝7.5。
Comparative example 1
Same as example 3 except that there is no distilled water treatment step, H2O/SiO214. The XRD pattern of the obtained sample is shown in FIG. 11, and the sample does not belong to ATS structure.

Claims (12)

1. An ATS type silicon-aluminum molecular sieve, the calcined form of the molecular sieve has a formula of SiO2·1/nAl2O3"wherein the molar ratio of Si to Al is 6. ltoreq. n.ltoreq.10, preferably 6.25. ltoreq. n.ltoreq.9.75, more preferably 6.5. ltoreq. n.ltoreq.9.5.
2. The ATS-type silicoaluminophosphate molecular sieve of claim 1, wherein: the ATS type silicon-aluminum molecular sieve has a strip shape or a bar shape, the average length of crystals is 0.6-1.8 mu m, and the length-width ratio is 2-20.
3. The ATS-type silicoaluminophosphate molecular sieve of claim 1, wherein: the acid content of B in the ATS type silicon-aluminum molecular sieve is not less than 500 mu mol/g, preferably 500-700 mu mol/g; the amount of the strong B acid is not less than 250 mu mol/g, preferably 250-350 mu mol/g; the total acid amount of the calcined ATS type silicon-aluminum molecular sieve is not less than 1000 mu mol/g, preferably 1000-1700 mu mol/g, and the strong acid amount is not less than 300 mu mol/g, preferably 300-400 mu mol/g.
4. The ATS-type silicoaluminophosphate molecular sieve of claim 1, wherein: the specific surface area of the ATS type silicon-aluminum molecular sieve is 200-600 m2Per gram, preferably 250 to 500 m2Per gram; the micropore volume of the ATS type silicon-aluminum molecular sieve is 0.05-0.30 cm3A/g, preferably 0.10 to 0.25 cm3Per gram.
5. A preparation method of an ATS type silicon-aluminum molecular sieve is characterized by comprising the following steps: mixing a silicon source, an aluminum source, a fluorine source, an organic structure directing agent and water, and then carrying out water steaming treatment; then carrying out crystallization reaction on the raw material mixture to obtain the ATS type silicon-aluminum molecular sieve;
wherein the added silicon source is SiO2Calculated by Al as the aluminum source2O3The molar ratio is 1 (0.08-0.17), preferably 1 (0.1-0.15); the organic structure directing agent is 4-pyrrolidinyl pyridine.
6. The method of claim 5, wherein: the added silicon source is SiO2The molar ratio of the fluorine source (F) to the organic structure directing agent to the water is 1 (0.05-2.0) (0.05-1.0) to (7.5-100), preferably 1 (0.1-1.8) (0.1-0.9) to (7.5-80), more preferably 1 (0.2-1.6) (0.2-0.8) to (7.5-60).
7. The method of claim 5, wherein: the silicon source is at least one of silicic acid, silica gel, silica sol, tetraethyl silicate and water glass; the aluminum source is selected from at least one of aluminum hydroxide, aluminum oxide, aluminate, aluminum salt and tetraalkoxy aluminum; the fluorine source is hydrofluoric acid.
8. The method of claim 5, wherein: the method for treating the distilled water comprises rotary evaporation water removal or open heating water removal, wherein the open heating treatment condition is heating and stirring at 35-90 ℃, preferably at 40-85 ℃.
9. The method of claim 5, wherein: after the raw material mixture is subjected to water evaporation treatment, a silicon source is SiO during crystallization2The molar ratio of the water to the water is 1 (1-5), preferably 1 (1.5-4.5).
10. The method of claim 5, wherein: the crystallization reaction is performed under the conditions of crystallization at 120-210 ℃ for 2-20 days, preferably at 130-195 ℃ for 3-18 days, and more preferably at 140-180 ℃ for 4-16 days.
11. A molecular sieve composition comprising the ATS-type silicoaluminophosphate molecular sieve of any one of claims 1 to 4 or the ATS-type silicoaluminophosphate molecular sieve synthesized according to the method of making the ATS-type silicoaluminophosphate molecular sieve of any one of claims 5 to 10, and a binder.
12. The use of the ATS-type aluminosilicate molecular sieve of any one of claims 1 to 4, the ATS-type aluminosilicate molecular sieve synthesized according to the method of preparing the ATS-type aluminosilicate molecular sieve of any one of claims 5 to 10, or the molecular sieve composition of claim 11 as an adsorbent or a catalyst.
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